JPH058415B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to color photographic materials. More specifically, the present invention relates to a color photographic material for printing, in which dye images are less likely to fade due to light and have a good color balance during fading. Prior art and its problems Conventionally, color photographic light-sensitive materials for printing include a blue-sensitive silver halide emulsion layer containing a yellow coupler, a non-light-sensitive first intermediate layer, and a magenta coupler on a reflective support. a green-sensitive silver halide emulsion layer containing a green-sensitive silver halide emulsion layer, a non-photosensitive second intermediate layer, a red-sensitive silver halide emulsion layer containing a cyan coupler,
It is formed by sequentially applying a non-photosensitive protective layer. In order to particularly suppress fading of the dye image due to light, an ultraviolet absorber is added to the first intermediate layer and/or the second intermediate layer. However, such conventional color photographic light-sensitive materials for printing are still insufficient in terms of image storage stability, particularly light resistance, and have the disadvantage that dye images are significantly faded by light. In particular, among the dye images formed from each coupler, the fading speed increases in the order of yellow, magenta, and cyan, and the difference is extremely large, resulting in a disadvantage that the color balance is greatly disrupted by light irradiation. This means that the British Journal of
It is also described in photography128 (6329) 1170-1171 (1981), etc. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide a color photographic material in which a dye image is less likely to fade due to light and has a good color balance in fading. be. As a result of various studies conducted for this purpose, the present inventors have found that the non-photosensitive layer located on the opposite side of the support to the cyan emulsion layer contains an ultraviolet absorber, and the ultraviolet absorber used And Cyan,
The present inventors have discovered that this object can only be achieved when magenta and yellow couplers are combined in specific ways, respectively, leading to the present invention. That is, the present invention provides a silver halide emulsion layer containing a yellow coupler represented by the following general formula [] and a silver halide emulsion layer containing a magenta coupler represented by the following general formula [] on a reflective support. A silver halide emulsion layer containing a cyan coupler represented by the following general formula [] is provided on the farthest side from the support, and further adjacent to the silver halide emulsion layer containing this cyan coupler, A first non-photosensitive layer is provided on the side opposite to the support side, and a second non-photosensitive layer is provided on the support side, and at least this first non-sensitive layer contains an ultraviolet absorber represented by the following general formula []. This is a color photographic material characterized by: General formula [] {In the above general formula [], R ₁ represents a hydrogen atom, a halogen atom, or an alkoxy group, and R ₂ represents -NHCOR ₂₁ , -NHSO ₂ R ₂₁ , -COOR ₂₁
or

[Formula] (wherein R ₂₁ and R ₂₂ each represent an optionally substituted alkyl group), and Z ₁ is an atom that is separated during coupling or a group that has a bond on the N atom. Represents a nitrogen heterocyclic group. } General formula [] {In the above general formula [], X ₁ is a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkoxy group, an aryloxy group, an amide group, a hydroxy group, a cyano group, or a nitro group, and Y ₁ , Y ₂ and Y ₃ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxy group, or an alkoxycarbonyl group. W ₁ represents a hydrogen atom, a halogen atom or a monovalent organic group, and Z ₂ represents an atom or group that is separated upon coupling. } General formula [] {In the above general formula [], R ₃ , R ₄ and R ₅ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, or an alkoxy group, R ₈ represents a hydrogen atom or an alkyl group, and Z ₃ represents an atom or group that is separated upon coupling. } General formula [] {In the above general formula [], R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group. } Specific constitution of the invention The color photographic light-sensitive material (hereinafter referred to as "sensitive material") of the present invention is
It has two or more silver halide emulsion layers, but in a typical embodiment, it has three types of light-sensitive silver halide emulsion layers with different spectral sensitivities, and each emulsion layer has diffusion-resistant yellow, magenta, and yellow emulsion layers. It contains one of three types of couplers: and cyan. In such a case, the combination of the light-sensitive silver halide emulsion layer and the coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a magenta coupler in the green-sensitive silver halide emulsion layer, Furthermore, a yellow coupler is respectively combined with the blue-sensitive silver halide emulsion layer. Then, such emulsion layers are coated on the reflective support in the following order: a yellow coupler-containing emulsion layer, a magenta coupler-containing emulsion layer, and a cyan coupler-containing emulsion layer, or a magenta coupler-containing emulsion layer, a yellow coupler-containing emulsion layer, etc. The emulsion layer and the cyan coupler-containing emulsion layer are coated in this order. The yellow coupler used in the present invention is at least one of the couplers represented by the above general formula [].
It is a seed. To explain the above general formula [ ] in more detail, R ₂ is -NHCOR ₂₁ , -NHSO ₂ R ₂₁ , -
COOR ₂₁ or

In the group represented by [Formula], R ₂₁ and R ₂₂ may each be an unsubstituted alkyl group, or substituted aryloxy group, alkoxycarbonyl group, alkylsulfonyl group, sulfonic acid group, aryl It may be an alkyl group substituted with a group, a substituted alkylamide group, or the like. Furthermore, Z ₁ represents a nitrogen-containing heterocyclic group having a bond at the N atom that is separated by various known couplings. Next, typical examples of the yellow coupler represented by the above general formula [] will be listed. These yellow couplers are disclosed in, for example, West German Published Patent No. 2057941, West German Published Patent No. 2163812,
JP-A-47-26133, JP-A-48-29432, JP-A-Sho
No. 50-65231, JP-A-51-3631, JP-A-51-
No. 50734, JP 51-102636, JP 51-33410
No., JP 48-66835, JP 48-94432, JP 49-1229, JP 49-10736, JP 52
It can be synthesized according to the method described in, for example, No.-25733. In addition to these couplers, other yellow couplers can also be used in combination. The magenta coupler used in the present invention is at least one of the couplers represented by the above general formula [].
It is a seed. To explain the general formula [] in more detail, W ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group, and examples of the monovalent organic group include a nitro group, an alkyl group, an alkoxy group, Acylamino group, sulfonamide group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylsuccinimide group, alkoxycarboxamido group, alkoxycarbamoyl group, each of which may have a substituent. Suitable examples include an alkylamino group, an aralkoxycarboalkylamino group, an alkylaminocarboalkylamino group, an arylaminocarboalkylamino group, and an aralkylaminocarboalkylamino group. Further, Z ₂ may be an atom or group that is separated by various known couplings. Next, a typical example of a magenta coupler represented by the general formula [] will be given. These magenta couplers are known, for example, from US Patent No. 3,684,514, British Patent No. 1,183,515,
-6031, Special Publication No. 6035, Special Publication No. 15754, Special Publication No. 15754
No. 45-40757, 1975-19032, 13041-1981, 129035-129035, 129035-1980
It can be synthesized according to the method described in No. 51-37646, JP-A No. 55-62454, etc. In addition to these couplers, other magenta couplers can also be used in combination. The cyan coupler used in the present invention is at least one type of coupler represented by the above general formula []. In the above general formula [ ], Z ₃ may be an atom or group that is separated by various known couplings. Next, typical specific examples of the cyan coupler represented by the above general formula [] will be given. These cyan couplers can be synthesized, for example, according to the methods described in US Pat. No. 2,423,730, US Pat. No. 2,801,71, and the like. In addition to these cyan couplers, other cyan couplers can also be used in combination. Each such coupler is contained in the silver halide emulsion layer in an amount of about 0.1 to 1 mole per mole of silver halide. On the other hand, a first non-photosensitive layer is provided adjacent to and above the silver halide emulsion layer containing a cyan coupler (on the side opposite to the support side). Further, a second non-photosensitive layer is provided below (on the support side) adjacent to the cyan coupler-containing emulsion layer, that is, between the cyan coupler-containing emulsion layer and the magenta or yellow coupler-containing layer. These first and second non-photosensitive layers consist of a hydrophilic binder, such as gelatin. At least the first non-photosensitive layer contains a benzotriazole-based ultraviolet absorber represented by the above general formula []. Next, typical specific examples of the ultraviolet absorbent represented by the above general formula [] will be shown. These benzotriazole compounds are disclosed in Japanese Patent Publications No. 36-10466, No. 42-26187, No. 48-5496,
No. 48-41572, U.S. Patent No. 3754919, U.S. Patent No. 4220711
It is stated in the number etc. In addition to such ultraviolet absorbers, other ultraviolet absorbers can also be used in combination. The ultraviolet absorber represented by the above general formula [] is contained in an amount of about 0.01 to 2 parts per 1 part by weight of the binder in the first non-photosensitive layer. Note that it is preferable that the ultraviolet absorber represented by the above general formula [] be contained in the second non-photosensitive layer in addition to the first non-photosensitive layer. In this case, the amount contained in the second non-photosensitive layer may be appropriately determined so as to obtain an appropriate color balance of light resistance, but
The amount contained in the non-photosensitive layer is preferably about 0.1 to 50, more preferably about 0.5 to 5. Furthermore, as the third non-photosensitive layer, a non-photosensitive layer may be provided between the emulsion layer on the support side and the emulsion layer above it. And this third
The compound represented by the above general formula [] or other ultraviolet absorbers can also be added to the non-photosensitive layer, if necessary. In addition, the first, second and third non-photosensitive layers may contain a color mixing inhibitor such as dioctylhydroquinone or dibutylhydroquinone, or a whiteness adjuster described in JP-A-55-93150, if necessary. , a coating aid, etc. may be contained. The amount of binder applied to each of the first and second non-photosensitive layers and the third non-photosensitive layer is usually about 1 to 30 mg/dm ² . On this premise, there are various methods for dispersing each diffusion-resistant coupler in the photosensitive material of the present invention, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. The method can be selected as appropriate depending on the chemical structure of the diffusion-resistant coupler, etc. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. . These dispersion methods have been well known, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open No. 74538/1983.
Publications No. 51-59943 and No. 54-32552 and Research Disclosure
Disclosure) Magazine, August 1976, No. 14850, 77-79
It is written on the page. Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)
Ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1
- homopolymers, copolymers and copolymers of monomers such as sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, etc. It is a terpolymer. Conventionally known methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method, such as N-butylacetanilide, diethyl lauramide, dibutyl phthalate, tricresyl phosphate, N- One method is to dissolve the above-mentioned diffusion-resistant coupler in a high boiling point solvent such as dodecylpyrrolidone and finely disperse it in a hydrophilic colloid such as gelatin. The silver halide used in the silver halide emulsion layer of the light-sensitive material of the present invention includes conventional silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Any used in silver halide photographic emulsions are included. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have an abnormal layered structure between the inside and the outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art. It is preferable that soluble salts be removed from the silver halide emulsions used in the light-sensitive materials of the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately. As the binder for the silver halide emulsion layer or the non-photosensitive layer, conventionally known binders are used.
Suitable examples include gelatin derivatives such as gelatin, phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin. These binders can be used as a compatible mixture of two or more if desired. A true silver halide emulsion in which silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers. As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used. In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can also be used together. As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds can be used. As selenium sensitizers, active and inactive selenium compounds can be used. Reduction sensitizers include monovalent tin salts, polyamines, bisalkyl group amino sulfides, silane compounds,
These include iminoaminomethane sulfuric acid, hydrazinium salts, and hydrazine derivatives. On the other hand, a conventionally known method may be used to incorporate the ultraviolet absorber into the non-photosensitive layer. That is, it is dissolved in a high boiling point organic solvent with a boiling point of approximately 175°C or higher, if necessary in combination with a low boiling point solvent, and then finely dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. It may be added to the desired hydrophilic colloid layer. To be more specific, examples of high boiling point solvents include organic acid amides, carbamates, esters, ketones, urea derivatives, etc., especially phthalates such as dimethyl phthalate, diethyl phthalate, dipropylphthalate, and dibutyl phthalate. Acid esters, phosphoric acid esters such as trimethylphosphate, triethylphosphate, tripropylphosphate, and tributylphosphate; sebasylate esters such as dioctyl sebacate, di-(2-ethylhexyl) sebacate, and diisodecyl sebacate. , glycerin esters such as glycerol tripropionate and glycerol tributyrate; in addition, adipic acid esters, glutaric acid esters, succinic acid esters, maleic acid esters, fumaric acid esters, citric acid esters, etc. are used. Then, add a UV absorber to these high boiling point solvents at the same time, as necessary, with methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide. , dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol, monoacetate, acetylacetone, nitromethane,
Dissolved in a low boiling point solvent such as nitroethane, carbon tetrachloride, chloroform (these high boiling point solvents and low boiling point solvents may be used alone or in combination), and alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acid, etc. Anionic surfactants and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate are mixed with an aqueous solution containing a hydrophilic binder such as gelatin, and mixed with a high-speed rotary mixer, colloid mill or ultrasonic. It may be emulsified and dispersed using a dispersion device or the like and added to the hydrophilic colloid. In addition to the above-mentioned additives, the photosensitive material of the present invention may also contain stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, DIR substances, optical brighteners, and other photographic additives. Various additives useful for photosensitive materials may be added. In addition to the silver halide emulsion layer and the non-photosensitive layer, the sensitive material of the present invention may be provided with a back layer or the like as appropriate. As the reflective support for the photosensitive material of the present invention, conventionally known supports such as plastic laminate paper, baryta paper, synthetic paper, etc. can be appropriately selected depending on the purpose of use, and these supports are generally used in the photographic emulsion layer. Various treatments may be applied to strengthen the adhesion. Specific Effects of the Invention The light-sensitive material of the present invention is exposed to light through a negative light-sensitive material having an image made of a coupling product, for example, and then subjected to color development processing. The color development process is carried out by a normal color development method. That is, first, it is processed with a color developing solution containing a color developing agent. Alternatively, a color developing agent or its precursor is contained in the sensitive material, and this is
Treated with so-called activator liquid. Thereafter, a bleaching step and a fixing step are usually performed according to conventional methods. In this case, the color development process using a color developer or activator liquid, the bleaching process, and the fixing process may be performed independently, but instead of performing two or more processes independently, a process that has these functions is used. It is also possible to carry out once (one bath) using a liquid. For example, a one-bath processing method in which a color developing solution or an activator solution contains both a bleaching agent and a fixing agent as described below, and a bleaching and fixing method in which bleaching and fixing are carried out after the color development step. Methods include using a bath. Also, after processing with a color developer or activator solution, desilvering can be carried out by immediately processing with a bleach-fixing bath, etc., but an acidic stop step is provided between the color development step and the bleaching and fixing steps. You can also do that. For such an acidic stop bath, an aqueous solution of acetic acid, citric acid, etc. can be used. Further, steps such as predural mater, neutralization, washing with water, stabilization, etc. can be provided as necessary. Through such color development processing, a dye image is formed on the print sensitive material by a coupling reaction. A typical color developing agent for the photosensitive material of the present invention is an aromatic primary amine color developing agent. Aromatic primary amine color developing agents include aminophenol derivatives and P-phenylenediamine derivatives, and these compounds can be used in the free state or as their hydrochlorides, sulfates, P-toluenesulfonates, Tetraphenylborate, P
It can be used as an organic acid salt such as -(t-octyl)benzenesulfonate. Specific aromatic primary amine color developing agents include O-aminophenol, P-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino -1,4-dimethylbenzene, N,N-diethyl-P-phenylenediamine hydrochloride, N-methyl-P-phenylenediamine hydrochloride, N,N-dimethyl-P-phenylenediamine hydrochloride, N- Ethyl-N-β-methanesulfonaminoethyl-3
-Methyl-4-aminoaniline and its sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, N,N-diethyl-3-(β-methanesulfonamidoethyl)-4-aminoaniline hydrochloride, 4 -amino-N-(2-methoxyethyl)
-N-Ethyl-3-methylaniline-P-toluenesulfonate, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaliline tetraphenylborate, 4-amino-N -(2-methoxyethyl)-N-ethyl-3-
Methylaniline tetraphenylborate, P
Typical examples include -morpholinoaniline, P-piperidinoaniline, 4-amino-N,N-diethyl-3-chloroaniline, and the like. In some cases, the photosensitive material of the present invention may contain
A color developing agent precursor may also be included. A color developing agent precursor is a compound that can form a color developing agent under alkaline conditions;
Examples include a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, a Schüger amine reactant precursor, and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat. No. 3,342,599, U.S. Pat.
Specifications of British Patent No. 803783, JP-A-53-
Publications No. 135628 and No. 54-79035, research
Disclosure Magazine No. 15159, No. 12146, No.
Described in No. 13924. These aromatic primary amine color developing agents are
It is usually contained in a color developing solution in an amount of about 1 to 20 g/approx. When it is contained as a precursor in a sensitive material, it is contained in an amount of about 0.5 to 3 moles per mole of silver halide. The color developing solution or activator solution used for the photosensitive material of the present invention includes alkaline agents such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, etc., and sulfurous acid. Sulfites such as sodium and potassium sulfite, sodium bromide, potassium bromide,
It contains bromide salts such as ammonium bromide. Furthermore, if necessary, a known development inhibitor,
Thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, chloride salts such as ammonium chloride, potassium chloride, sodium chloride, ethylene glycol, diethylene glycol, methanol, ethanol, n
-butanol, benzyl alcohol, acetone,
Organic solvents such as dimethylformamide, amines such as hydroxylamine, ethanolamine, ethylenediamine, diethanolamine, water softeners such as sodium hexametaphosphate, sodium tripolyphosphate, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and water-soluble optical brighteners. May be contained. The color developing solution or activator solution used in the present invention may contain an auxiliary developer. As such an auxiliary developer, 1-aryl 3-pyrazolidone derivatives are preferred, and are used in an amount of 1 mg to 1 g, preferably 10 mg to 500 mg, per color developer or activator solution.
A typical auxiliary developer is 1-phenyl-3
-pyrazolidone, 4-methyl-1-phenyl-3
-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone,
4-Methyl-4-hydroxymethyl-1-(P-
and tolyl)-3-pyrazolidone. The color developing solution or activator solution used in the present invention is kept alkaline according to a conventional method, and its hydroxyl ion concentration is determined depending on the type, composition, purpose, and use of the print sensitive material of the present invention to be processed. Therefore, it can be selected as appropriate, but PH9.5 to 13.5 is common. The color developing solution or activator solution used in the present invention is generally used within a certain temperature range. The temperature range can be appropriately selected depending on the type, composition, use, purpose, etc. of the printed photosensitive material according to the present invention to be processed, but is preferably 15°C to 70°C, more preferably 30°C to 50°C. As the bleaching agent used in the bleaching or bleach-fixing bath, known compounds can be used, such as ferric complex salts of aminopolycarboxylic acids such as ferric sodium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, Persulfates such as ammonium sulfate and sodium persulfate can be used. Further, as the fixing agent used in the fixing or bleach-fixing bath, known compounds can be used, such as thiosulfates such as sodium thiosulfate and ammonium thiosulfate, 3,6-dithia-
Water-soluble sulfur-containing diols such as 1,8-octanediol, 3,6,9,12-tetrathia-1,14-tetradecanediol, ethylene-bis-thioglycolic acid, ethylene-bis-thioglycolic acid sodium salt Water-soluble sulfur-containing dibasic acids such as the following can be used. Specific Effects of the Invention According to the present invention, the light fastness of the dye image formed is improved, and fading due to light is significantly reduced.
In particular, the color balance of fading due to light is extremely good. Such an effect occurs only when specific yellow, magenta, and cyan couplers and ultraviolet absorbers are used in combination. Furthermore, according to the present invention, fogging on static during coating manufacturing and transportation within a printer is also extremely effectively prevented. In order to confirm the effects of the present invention, the present inventors
Various experiments were conducted. An example is shown below. Example 1 The following layers 1 to 6 were coated on a reflective support consisting of polyethylene coated paper. 1st layer...A blue-sensitive silver chlorobromide emulsion and an emulsified dispersion of a yellow coupler. 2nd layer...An intermediate layer containing an emulsified dispersion of 2,5-ditertiary-octylhydroquinone. 3rd layer...A green-sensitive silver chlorobromide emulsion and a magenta emulsion. 4th layer of emulsified dispersion of coupler... Intermediate layer containing emulsified dispersion of 2,5-ditertial octylhydroquinone and an ultraviolet absorber 5th layer... Emulsified dispersion of red-sensitive silver chlorobromide emulsion and cyan coupler 6th layer Layer...Non-photosensitive layer containing an emulsified dispersion of an ultraviolet absorber In this case, as the yellow, magenta and cyan couplers and the ultraviolet absorber, those shown in Table 1 below are used in the amounts shown in the table. Using. In the table, the types of yellow, magenta, and cyan couplers and ultraviolet absorbers are indicated by the numbers of the above-mentioned compound examples. In addition, the following yellow coupler Y', magenta coupler M', cyan coupler C', and ultraviolet absorber UV' were used for comparison. When adding the ultraviolet absorber, dibutyl phthalate was used as a high boiling point solvent. A coating aid and a hardening agent were added to each of these layers to obtain samples Nos. 1 to 13 shown in Table 1.

【table】

[Table] Samples Nos. 1 to 13 prepared in this manner were subjected to optical wedge exposure, and then subjected to the processing shown below to obtain gray images. Processing process (32.8℃) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 3 minutes 30 seconds drying Color developer composition

[Table] Bleach-fix solution composition Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water to 1 and adjust to pH 7.0 using oxidation. Oxidation-reduction potential -70mV Next, the gray image of each sample obtained in this way was irradiated with a xenon fademeter of 30,000 lux for 300 hours, and then a Sakura color densitometer PDA-60 model (Konishi Roku Photo Industry Co., Ltd.) was used. company)
The change in density 1.0 in each dye image was measured. The measured values are shown in Table 2 below as light resistance.
Shown below.

[Table] From the results shown in Table 2, the above general formula []
Only when the yellow, magenta, and cyan couplers represented by [] and [] are combined with the ultraviolet absorber represented by the above general formula [], the light fastness of each dye image becomes extremely good. Furthermore, it can be seen that the color balance of fading is also improved. It has been confirmed that even if these yellow, magenta, cyan couplers, and ultraviolet absorbers are replaced with other compounds represented by the above general formulas, the same effect can be achieved. Example 2 Samples Nos. 14, 15, and 16 were prepared in the same manner as Sample No. 1 except that the ultraviolet absorber was used as shown in Table 3.
Two samples were made.

[Table] Each of these samples was tested for light resistance in the same manner as in Example 1. The results are shown in Table 4.

[Table] According to the results in Table 4, the ultraviolet absorber represented by the general formula [] was added to the silver halide emulsion layer containing a cyan coupler, but was not added to the adjacent 6th layer, which is a non-photosensitive layer. Sample without (sample No. 14)
Although cyan coupler is added to the silver halide emulsion layer containing a cyan coupler, it causes large fading of the cyan dye and poor balance of fading of yellow magenta and cyan dyes, but it is added to the adjacent non-photosensitive layer 6. (Sample No. 15 and
16), it can be seen that the fading balance of yellow, magenta and cyan dyes is clearly improved. <Comparative experiment> The amount of UV' in the 6th layer of sample No. 9 of Example 1 was 3
A test green similar to Sample No. 9 was prepared except that the amount was increased from mg/dm ² to 6 mg/dm ² (sample No. 9'). A sample similar to Sample No. 9 was prepared except that the UV' layer in the layer was replaced with a comparative ultraviolet absorber (UV'') having the structure shown below.
(Sample No. 17) Furthermore, the UV' of the 6th layer of Sample No. 9 of Example 1 was
A sample similar to sample No. 9 was prepared except that the amount added was 6 mg/dm ² instead of UV''. (Sample No. 17') Each of these samples was tested for light resistance in the same manner as in Example 1. The results are shown in Table-5.

[Comparative experiment 2]

The following four samples were prepared according to sample No. 3 of Example 1. UV of the 6th layer and 4th layer of sample No. 3 of Example 1
The same sample as Sample No. 3 was prepared, except that -7 was replaced with UV' and C-9 in the fifth layer was replaced with C'. (Sample No. 18) UV of the 6th layer and 4th layer of Sample No. 3 of Example 1
The same sample as sample No. 3 was prepared except that -7 was replaced with UV'. (Sample No. 19) UV of the 6th layer and 4th layer of Sample No. 3 of Example 1
The same sample as Sample No. 3 was prepared except that -7 was replaced with UV' and M-19 in the third layer was replaced with M'.
(Sample No. 20) UV of the 6th layer and 4th layer of Sample No. 3 of Example 1
The same sample as Sample No. 3 was prepared except that -7 was replaced with UV' and Y-7 in the first layer was replaced with Y'.
(Sample No. 21) Each of these samples was tested for light resistance in the same manner as in Example 1. The results are shown in Table-6.

[Table] By comparing the difference in light fastness between the cyan dye images of sample No. 18 and sample No. 19 and the difference in light fastness between the cyan dye images of sample No. 6 and sample No. 3 (invention),
C′ as cyan coupler, as ultraviolet absorber
When using UV' and C- as a cyan coupler.
9. Compared to the case where UV' is used as a cyan coupler and UV-7 is used as a cyan coupler and UV-7 is used as a cyan coupler and UV' is used as a cyan coupler and UV' is used as an ultraviolet absorber. -7
It can be seen that there is a large difference compared to when using . Similarly, the difference in light fastness between magenta dye images of sample No. 20 and sample No. 19, and sample No. 5 and sample No. 3 (invention)
By comparing the difference in light fastness of magenta dye images, we found that when M′ was used as a magenta coupler and UV′ was used as an ultraviolet absorber, and when M-19 was used as a magenta coupler and UV′ was used as an ultraviolet absorber. Compared to the difference, there is a large difference between using M' as the magenta coupler and UV-7 as the UV absorber and using M-19 as the magenta coupler and UV-7 as the UV absorber. I understand. Also, the difference in light fastness between the yellow dye images of sample No. 21 and sample No. 19, and the difference in light resistance between sample No. 4 and sample No. 3 (invention)
By comparing the difference in light fastness of the yellow dye images of There is a large difference between using Y' as a yellow coupler and UV-7 as an ultraviolet absorber and using Y-7 as a yellow coupler and UV-7 as an ultraviolet absorber. I understand.

Claims (1)

[Scope of Claims] 1. A silver halide emulsion layer containing a yellow coupler represented by the following general formula [] and a silver halide emulsion layer containing a magenta coupler represented by the following general formula [] on a reflective support. and a photographic emulsion layer containing a cyan coupler represented by the following general formula [] is provided on the farthest side from the support, and further adjacent to the silver halide emulsion layer containing this cyan coupler, A first non-photosensitive layer is provided on the side opposite to the support side, a second non-photosensitive layer is provided on the support side, and at least this first non-photosensitive layer and the second non-photosensitive layer are provided.
A color photographic material, characterized in that the non-photosensitive layer contains an ultraviolet absorber represented by the following general formula []. General formula [] {In the above general formula [], R ₁ represents a hydrogen atom, a halogen atom, or an alkoxy group, and R ₂ represents -NHCOR ₂₁ , -NHSO ₂ R ₂₁ , -COOR ₂₁
or [Formula] (wherein R ₂₁ and R ₂₂ each represent an optionally substituted alkyl group), and Z ₁ is a nitrogen-containing hetero compound having a bond on the N atom to be separated during coupling. Represents a ring group. } General formula [] {In the above general formula [], X ₁ is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkoxy group, aryloxy group, amide group, hydroxy group, cyano group, or nitro group, and Y ₁ , Y ₂ and Y ₃ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxy group, or an alkoxycarbonyl group. W ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group, and Z ₂ represents an atom or group that is separated upon coupling. } General formula [] {In the above general formula [], R ₃ , R ₄ and R ₅ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group, and R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, or an alkoxy group, R ₈ represents a hydrogen atom or an alkyl group, and Z ₃ represents an atom or group that is separated upon coupling. } General formula [] {In the above general formula [], R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. }